Purification of gases



April 9, 1940. v. vooRHEEs PURIFICATION 0F GASES vINVENTOR Filed Oct. 25, 1937 Patented Apr. 9, 1940l UNITED STATES PATENT oI-Flcav amaai rUmFIcA'noNoF Gases- Vanderveer Voorhees, Hammond, Ind., assignor to Standard Oil Company, Chicago, Ill., a corporation o! In Application October 25, 1937, Serial No. 170,747

5 Claims. (Cl. 23-2) y l to provide a continuous process oi removing hydrogen sulde by absorption in a chemicalV reagent wherein the reagent may be used repeatedly with a minimum loss in the process. Still another object of the invention is to provide 15 a new absorbing reagent for removal of carbon dioxide, hydrogen sulfide and other weakly acidic gaseous substances, which reagent possesses certain advantages over reagents employed heretofore.

20 The reagent which I employ in my process is an alkali salt of a mono chlorinated derivative of phenol of the class consisting of ortho chlorphenol, para ehlorphenol and meta ehlorphenol. I prefer to employ the sodium salts of the mono 25 chlorphenols, but I may also employ the potassium salts or other water soluble salts of the chlorphenols with strong bases, or mixtures thereof. Of the three mono chlorphenols, I prefer to employthe ortho and para derivatives, and particularly a mixture of ortho ehlorphenol and para ehlorphenol. A mixture containing about 60% of para ehlorphenol and about 40% of ortho chlorphenol is suitable, although various other compositions may be employed in which the amount of ortho compound may constitute from about 20% to about 80% of the total. The mixture may be contaminated with small amounts of other phenols, for example from 2% to 10% of cresol, phenol, dichlorphenol, etc., may be present without departing from the spirit of my invention. In conducting the process` I prefer to employ a solution of ehlorphenol and sodium hydroxide wherein the proportion of sodium hyldroxide to ehlorphenol is approximately equimolecular, or the solution may contain a slight excess of the ehlorphenol. Too great an yexcess of the ehlorphenol reduces the capacity of the solution for absorbing hydrogen sulilde and may 50 unnecessarily complicate the regeneration of the solution.

The accompanying drawing which forms a part of this specification shows diagrammatically one form of an apparatus suitable for carrying out u the process. Referring to the drawing. 88s con- One of the f order to compensate for unavoidableloss of solutaining hydrogen sulfide, for example refinery gas, blast furnace gas, coke oven gas, etc., which may contain-about 0.1% to about by volume of HzS, may be introduced by line I0 into scrubber ,p I I where it is brought into intimate contact with 5 descending treating solution introduced into the scrubber by line I2. Treated gas substantially' free from hydrogen sulde is withdrawn by line I3 leading to gas main Il.

Treating solution containing dissolved hydrogen sulfide is Withdrawn from the scrubber II by line I5 and pump I6, heated by passing through heat exchanger .I1 and thence by line I8 isintroduced into regenerator I9. Regenerator I9 is a combination fractionating and stripping 15 tower, the upper section preferably being supplied with bubble plates and the lower section with bailles or bubble plates to provide emcient stripping. Stripping gas, for example flue gas, air or steam, may be introduced by line at the 20 base of the regenerator and heat may be supplied to the solution in the base of the regenerator by closed steam heating coil 2|. Cooling may -be supplied at the top of the regenerator by reflux coil 22 which serves to condense a 'portion 25 of the water and any mono ehlorphenol which may be carriedupward through the regenerator. Hydrogen sulde which is driven oi from the solution in regenerator I9 by the combined action of stripping gas and heat is conducted by line 3" 23 to vent 24 or it may be conducted by line 25 to condenser 26 where it is cooled further to condense water andtraces of mono ehlorphenol which may be carried over and which are collected in receiver 21. Any amount of mono ehlorphenol thus collected may be separated fromthe water and returned to the system as provided hereinafter. If desired, a reduced pressure may be supplied. by suitable vacuum pump to regenerator I9 to assist in liberation of hydrogen sulfide 4 from the solution. f

The hot :regenerated solution .is withdrawn from the bottom of I9 by line 28 and pump 29 and passes through heat exchanger yI 'l and thence by line 30 to cooler 3| where the temperature is reduced to a conveniently low temperature obtainable by the cooling water, for example '70' to 90 F. The cooled solution then flows by line I2 to absorber I-I as previously described. In 50 tion which may'occur by mechanical leakage, etc., additional ehlorphenol from supplytank 32 and sodium hydroxide solution from tank 33 are conducted by lines 34 and 35 respectively to u mixer I6 where the desired sodium chlorphenolate is produced which is delivered by line 31 into circulating line I2. The desired ratio of chlorphenol and sodium hydroxide in the circulating solution may also be altered by introducing either constituent to the stream by the same means. The total concentration of sodium chlorphenolate in the circulating aqueous solution may be varied over a considerable range, but it is preferred to employ a concentration of about 20% to about If the solution becomes too dilute by condensation of moisture from the gas introduced by line I0 I may restore theconcentration Veither by adding additional more-concentrated solution by line 31 or by withdrawing water vapor from the regenerator I9 by line 23 which may be controlled by regulating the temperature of reflux coil 22. However, column I9 may be operated in such a manner that some chlorphenol is carried over with the water vapor and condensed in condenser 26, in which case the dilute solution of chlorphenol and water may be` returned to the system by lines 42 and 38. Water may also be introduced by this means to dilute the solution when desired.

The operation of my process and similar processes depends on the ready hydrolysis of the solution in the absorber I I with the formation of free sodium hydroxide'which is available for absorbing hydrogen sulde by the formation of sodium hydrogen sulde, NaHS. The sodium hydrogen sulde is subsequently decomposed in regenerator I9 at the higher temperature under which conditions hydrogen sulde is volatilized from the solution, thus shifting the equilibrium in the direction of reforming sodium chlorphenolate. chlorphenol plays therole of a weak acid of high boiling point which yields sodium hydroxide to the hydrogen sulfide in the absorber and regains the sodium hydroxide in the regenerator without itself being removed from theprocess'. It is obvious that an acid, in order to `be successfully employed in the process, must produce a hydrogen ion concentration-in the solution. within a relatively narrow range; otherwise, if'l the hydrogen ion concentration is too high the solution will not efficiently absorb the HzS and if too low, too great heating will be required in the regenerator to force out the hydrogen sulde. I have discovered that the mono chlorphenols ionize within an advantageous range for this process, providing a maximum removal of HzS from the gases treated and a maximum ease of regeneration.

In one manner of operating my process I may employ a suiiicient excess of mono chlorphenol in the solution to eiect a fractionation of mono introduced into the base of the regenerator I9' by line 43 as desired, assisting in maintaining the The proper equilibrium conditions for removal of hydrogen sulfide.

Having thus described my process, what I claim is:

1. The process of removing weakly acidic gas from a gaseous mixture, which comprises contacting said gaseous mixture with an aqueous alkaline solution of monochlorphenol containing ortho and para monochlorphenol in the proportion of about 20% to about 80% of ortho monochlorphenol, withdrawing and heatingvsaid solution to regenerate it, then cooling and returning it to said contacting step.

2. The process of removing hydrogen sulfide from fuel gases which comprises intimately contacting said fuel gases with a solution of monochlorphenol and sodium hydroxide, wherein said monochlorphenol comprises para monochlorphenol and about 20% to about 80% of ortho monochlorphenol, absorbing said hydrogen sulfide in said solution, transferring said solution to a regenerating zone wherein it is subjected to heating and stripping to remove dissolved hydrogen sulfide and then cooling the regenerated solution and returning it to said contacting step.

3. In the process of removing weakly acidic gases such as HzS and CO2 from fuel gas mixtures wherein the gas is intimately contacted .with a solution of sodium monochlorphenolate containing ortho and para. monochlorphenol in the proportion of about 20% to about 80%'of ortho monochlorphenol, said weakly acidic gases are subsequently removed from the spent solution by heating and stripping and the regenerated solution is recirculated to the contacting step, the improvement comprising employing an excess of .chlorphenol in said sodiumichlorphenolate solution, distilling said excess monochlorphenol from said solution in said regenerating step, condensf ing said distilled monochlorphenol and returning it to said spent sodium chlorphenolate solution entering said regenerating step.

4. The process of removing weakly acidic gas such as HzS and CO2 from a gaseous mixture phenol in the ratio of about 40% of ortho mono- A' chlorphenol and 60% of para monochlorphenol,

withdrawing and heating said solution to regen,- erate it, then cooling and returning it to said contacting step.

`5. The process of removing hydrogen sulde from fuelgases which comprises intimately contacting said fuel gases at ordinary temperatures with an aqueous alkaline solution of monochlorphenol in which ortho and para monochlorphenol predominate and wherein ortho monochlorphenol constitutes from about 20% to about 80% of the total, absorbing said hydrogen sulfide in' said solution, transferring said solution to a regenerat- `ing zone wherein it is subjected to heating and stripping and dissolved hydrogen sulde is removed, cooling the regenerated solution and returning it to said contacting step.

vANDERVEER VOORHEES. 

